Production of and drying of copolymer fibers

ABSTRACT

The present invention concerns processes for reducing water in never-dried fiber comprising copolymer derived from the copolymerization of para-phenylenediamine, 5(6)-amino-2-(p-aminophenyl)benzimidazole; and terephthaloyl dichloride, the process having the following steps in a continuous process, (a) a step of drying a never-dried fiber having at least 0.1% sulfur at less than 150° C. until the moisture content of the fiber is less than 60 weight percent; and (b) a step of further drying the fiber above 150° C. while the moisture content of the fiber is no more than 60 weight percent; and the fiber being further heated to at least 350° C. in either an additional continuous or separate step.

TECHNICAL FIELD

The present application concerns methods of producing and dryingcopolymer fibers.

BACKGROUND

Advances in polymer chemistry and technology over the last few decadeshave enabled the development of high-performance polymeric fibers. Forexample, liquid-crystalline polymer solutions of heterocyclic rigid-rodpolymers can be formed into high strength fibers by spinningliquid-crystalline polymer solutions into dope filaments, removingsolvent from the dope filaments, washing and drying the fibers; and ifdesired, further heat treating the dried fibers. One example ofhigh-performance polymeric fibers is para-aramid fiber such as poly(paraphenylene terephthalamide) (“PPD-T” or “PPTA”).

Fiber strength is typically correlated to one or more polymerparameters, including composition, molecular weight, intermolecularinteractions, backbone, residual solvent or water, macromolecularorientation, and process history. For example, fiber strength typicallyincreases with polymer length (i.e., molecular weight), polymerorientation, and the presence of strong attractive intermolecularinteractions. As high molecular weight rigid-rod polymers are useful forforming polymer solutions (“dopes”) from which fibers can be spun,increasing molecular weight typically results in increased fiberstrength.

Fibers derived from 5(6)-amino-2-(p-aminophenyl)benzimidazole,para-phenylenediamine and terephthaloyl dichloride are known in the art.Hydrochloric acid is produced as a by-product of the polymerizationreaction. The majority of the fibers made from such copolymers havegenerally been spun directly from the polymerization solution withoutfurther treatment. Such copolymers are the basis for a high strengthfibers manufactured in Russia, for example, under the trade names Armos®and Rusar®. See, Russian Patent Application No. 2,045,586. However, thecopolymer can be isolated from the polymerization solvent and thenredissolved in another solvent, typically sulfuric acid, to spin fibers.

Previously, it was not appreciated that fibers derived from copolymersof 5(6)-amino-2-(p-aminophenyl)benzimidazole, para-phenylenediamine andterephthaloyl dichloride are prone to thermal damage when drying in acontinuous process even at low drying temperatures. This thermal damagecan create yarns having depressed tensile properties. Therefore, what isneeded are new methods to dry and further heat treat these copolymerfibers without damage.

Known processes for making copolymer fibers directly from polymerizationsolution, while producing a good product for use in ballistic and otheraramid end-uses, are very expensive with very poor investment economics.As such, there is a need in the art for manufacturing process whereinthe copolymer is solutioned in a common solvent, such as sulfuric acidwhich has both improved economics compared to processes known in the artand provides copolymer fibers having superior long-term physicalproperties.

SUMMARY

In some embodiments, the invention concerns processes for reducing waterin never-dried fiber comprising copolymer derived from thecopolymerization of para-phenylenediamine,5(6)-amino-2-(p-aminophenyl)benzimidazole; and terephthaloyl dichloride.The processes having the following steps in a continuous process: (a) astep of drying a never-dried fiber having at least 0.1 wt % sulfur at150° C. or less until the moisture content of the fiber is less than 60weight, and (b) a step of further drying the fiber above 150° C. whilethe moisture content of the fiber is less than 60 weight percent. Theresulting dried fiber is further heated to at least 350° C. in either anadditional continuous or separate step. In some embodiments, the fiberin step (a) is dried at 100° C. or less or at 50° C. or less.

In certain embodiments, in step (a) the fiber is dried until themoisture content is less than 50%. In some processes, in step (a) thefiber is dried until the moisture content is less than 40%

Additional processes steps may occur between steps (a) and (b) and/orbetween step (b) and the further drying step. In some embodiments, afterstep (a), the fiber is further dried at an additional step at less than150° C. until moisture content is less than 50%, prior to step (b). Inother embodiments, after step (a) the fiber is further dried at anadditional step at less than 150° C. until moisture content is less than40%, prior to step (b).

In certain processes, in step (a) the fiber is heated to 30° C. orgreater. In other processes, in step (a) the fiber is heated to 40° C.or greater.

The heating in step (a) may performed until the fiber has a moisturecontent of 6 weight percent or less in some embodiments of theinvention. In some embodiments, step (a) is carried out in less than tenminutes. In other embodiments, step (a) is carried out in less than 180seconds.

In regard to the further heating step, the filaments are heated above400° C. in the last step.

Tension may be applied to the filaments during heating steps. In somepreferred embodiments, the filaments are heated in step (a) under atension of at least 0.11 gpd. In certain preferred embodiments, thefilaments are heated in the last step under a tension of 1 gpd or less.

Preferred copolymers include those derived from the copolymerization ofpara-phenylenediamine, 5(6)-amino-2-(p-aminophenyl)benzimidazole; andterephthaloyl dichloride. In some embodiments, the ratio of moles of5(6)-amino-2-(p-aminophenyl)benzimidazole to the moles ofpara-phenylenediamine is 30/70 to 85/15. In other embodiments, the ratiois 45/55 to 85/15. For some copolymers, the ratio of (a) the moles ofpara-phenylenediamine and 5(6)-amino-2-(p-aminophenyl)benzimidazole to(b) the moles of terephthaloyl dichloride is 0.9-1.1.

Any practical heating method may utilized. In some processes the heatingis accomplished by contacting said yarn with heated gas. Heated gas maybe any gas that does not damage the yarn. Examples of heated gas includeair and nitrogen. The heated gas may be within an oven in step (a).Alternatively, the filaments are heated by contacting said filamentswith a hot surface.

Another aspect of the invention concerns processes for producingfilaments comprising a copolymer derived from the copolymerization ofpara-phenylenediamine, 5(6)-amino-2-(p-aminophenyl)benzimidazole; andterephthaloyl dichloride, including the following steps in a continuousprocess:

(a) a step of spinning filaments into a coagulation bath from a sulfuricacid solution of the copolymer;

(b) a step of contacting the filaments with one or more of (i) wash and(ii) neutralization fluid; and

(c) a step of drying a never-dried fiber having at least 0.1% sulfur at150° C. or less until the moisture content of the fiber is less than 60weight percent;

(d) an optional step of further drying the fiber at a temperature higherthan step (c);

(e) a step of further drying the fiber above 150° C. while the moisturecontent of the fiber is no more than 60 weight percent;

the fiber being further heated to at least 350° C. in either anadditional continuous or separate step. In some embodiments, thefilaments are heated above 400° C. in the last step.

In some embodiments, the combination of steps (c) and (d) is carried outin less than ten minutes. In yet other embodiments, the combination ofsteps (c) and (d) is carried out in less than 180 seconds.

In certain embodiments, the filaments are heated in step (c) under atension of at least 0.1 gpd. In certain embodiments, the filaments areheated in the last step under a tension of less than 1 gpd. In regard toheating temperatures, in step (c) the fiber is heated to 30° C. orgreater or to 40° C. or greater. In some preferred embodiments, in step(c) or (d) the fiber is heated until the moisture content is 6 weightpercent or less.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing summary, as well as the following detailed description, isfurther understood when read in conjunction with the appended drawings.For the purpose of illustrating the invention, there is shown in thedrawings exemplary embodiments of the invention; however, the inventionis not limited to the specific methods, compositions, and devicesdisclosed. In the drawings:

FIG. 1 is a schematic diagram of a fiber production process.

FIG. 2 presents a plot of yarn relative tenacity versus first dryingroll temperature.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present invention may be understood more readily by reference to thefollowing detailed description taken in connection with the accompanyingfigures and examples, which form a part of this disclosure. It is to beunderstood that this invention is not limited to the specific devices,methods, conditions or parameters described and/or shown herein, andthat the terminology used herein is for the purpose of describingparticular embodiments by way of example only and is not intended to belimiting of the claimed invention.

As used in the specification including the appended claims, the singularforms “a,” “an,” and “the” include the plural, and reference to aparticular numerical value includes at least that particular value,unless the context clearly dictates otherwise. When a range of values isexpressed, another embodiment includes from the one particular valueand/or to the other particular value. Similarly, when values areexpressed as approximations, by use of the antecedent “about,” it willbe understood that the particular value forms another embodiment. Allranges are inclusive and combinable. When any variable occurs more thanone time in any constituent or in any formula, its definition in eachoccurrence is independent of its definition at every other occurrence.Combinations of substituents and/or variables are permissible only ifsuch combinations result in stable compounds.

By “never-dried” it is meant the moisture content of the fiber is atleast 75 weight percent of the fiber.

The present invention is related to a process which performs thepolymerization of 5(6)-amino-2-(p-aminophenyl)benzimidazole,para-phenylenediamine and terephthaloyl dichloride at high solids (7weight percent or greater) in NMP/CaCl₂ or DMAC/CaCl₂, isolates thecopolymer crumb, dissolves the isolated copolymer crumb in concentratedsulfuric acid to form a liquid crystalline solution, and spins thesolution into fibers. By “solids” it is meant the ratio of the mass ofcopolymer to the total mass of the solution, that is, the mass of thecopolymer plus solvent.

The copolymerization reaction of5(6)-amino-2-(p-aminophenyl)benzimidazole, para-phenylenediamine andterephthaloyl dichloride can be accomplished by means known in the art.See, for example, PCT Patent Application No. 2005/054337 and U.S. PatentApplication No. 2010/0029159. Typically, one or more acid chloride(s)and one or more aromatic diamine(s) are reacted in an amide polarsolvent such as N,N-dimethylformamide, N,N-dimethylacetamide,N-methyl-2-pyrrolidone, dimethylimidazolidinone and the like.N-methyl-2-pyrrolidone is preferred in some embodiments.

In some embodiments, before or during the polymerization, a solubilityagent of an inorganic salt such as lithium chloride or calcium chloride,or the like is added in a suitable amount to enhance the solubility ofthe resulting copolyamide in the amide polar solvent. Typically, 3 to10% by weight relative to the amide polar solvent is added. After thedesired degree of polymerization has been attained, the copolymer ispresent in the form of an un-neutralized crumb. By “crumb” it is meantthe copolymer is in the form of a friable material or gel that easilyseparates into identifiable separate masses when sheared. Theun-neutralized crumb includes the copolymer, the polymerization solvent,the solubility agent and the byproduct water and acid from thecondensation reaction, typically hydrochloric acid (HCl).

After completing the polymerization reaction, the un-neutralized crumbis then contacted with a base, which can be a basic inorganic compound,such as sodium hydroxide, potassium hydroxide, calcium hydroxide,calcium oxide, ammonium hydroxide, and the like. The basic inorganiccompound can be used in aqueous solution to perform a neutralizationreaction of the HCl by-product. If desired, the basic compound can be anorganic base such as diethyl amine or tributyl amine or other amines.Typically, the un-neutralized copolymer crumb is contacted with theaqueous base by washing, which converts the acidic byproduct to a salt(generally a sodium chloride salt if sodium hydroxide is the base andHCl is the acidic byproduct) and also removes some of the polymerizationsolvent. If desired, the un-neutralized copolymer crumb can beoptionally first washed one or more times with water prior to contactingwith the basic inorganic compound to remove excess polymerizationsolvent. Once the acidic byproduct in the copolymer crumb isneutralized, additional water washes can be employed to remove salt andpolymerization solvent and lower the pH of the crumb, if needed.

This invention also relates to a process for forming an aramid yarncomprising dissolving a copolymer crumb derived from thecopolymerization of para-phenylenediamine,5(6)-amino-2-(p-aminophenyl)benzimidazole; and terephthaloyl dichloridein sulfuric acid to form a spinning solution, wherein the copolymercrumb is neutralized prior to forming said spinning solution; saidcopolymer having an inherent viscosity of at least 3 dl/g and havingless than 0.4 mol/Kg of titrate-able acid. In one preferred embodiment,the copolymer crumb is neutralized by washing with an aqueous base.Terephthaloyl dichloride is also known as terephthaloyl chloride.

The copolymer is preferably spun into fiber using solution spinningGenerally this involves solutioning the neutralized copolymer crumb in asuitable solvent to form a spin solution (also known as spin dope), thepreferred solvent being sulfuric acid. The inventors have found that theuse of copolymer crumb that has been neutralized as described hereindramatically reduces the formation of bubbles in the spin dope when suchneutralized crumb is combined with sulfuric acid in the solutioningprocess. If the copolymer crumb is not neutralized, the hydrochloricacid by-product in the copolymer will volatize on contact with thesulfuric acid and form bubbles in the spin dope. Since the solutionviscosity of the spin dope is relatively high, any such bubbles that areformed during solutioning tend to stay in the spin dope and are spuninto the filaments. The neutralized copolymer crumb, when solutioned insulfuric acid, provides an essentially bubble-free and therefore moreuniform spinning solution which is believed to provide more uniformlysuperior copolymer filaments and fibers.

The spin dope containing the copolymer described herein can be spun intodope filaments using any number of processes; however, wet spinning and“air-gap” spinning are the best known. The general arrangement of thespinnerets and baths for these spinning processes is well known in theart, with the figures in U.S. Pat. Nos. 3,227,793; 3,414,645; 3,767,756;and 5,667,743 being illustrative of such spinning processes for highstrength polymers. In “air-gap” spinning the spinneret typicallyextrudes the fiber first into a gas, such as air and is a preferredmethod for forming filaments

It is believed that in addition to producing the spinning dope withneutralized copolymer crumb, for the best fiber properties, themanufacturing process of spinning fibers from an acid solvent shouldadditionally include not only steps that extract acid solvent from thedope filaments but also further remove and/or neutralize any remainingacid associated with or bound to the copolymer in the fiber. It isbelieved that failure to do this can result in more potentialdegradation of the copolymer in the fiber and subsequent decrease infiber mechanical properties over time.

One process for making copolymer filaments or yarns is shown in FIG. 1.The dope solution 2, comprising copolymer and sulfuric acid, typicallycontains a high enough concentration of polymer for the polymer to forman acceptable filament 6 after extrusion and coagulation. When thepolymer is lyotropic liquid-crystalline, the concentration of polymer inthe dope 2 is preferably high enough to provide a liquid-crystallinedope. The concentration of the polymer is preferably at least about 7weight percent, more preferably at least about 10 weight percent andmost preferably at least about 14 weight percent.

The polymer dope solution 2 may contain additives such as anti-oxidants,lubricants, ultra-violet screening agents, colorants and the like whichare commonly incorporated.

The polymer dope solution 2 is typically extruded or spun through a dieor spinneret 4 to prepare or form the dope filaments 6. The spinneret 4preferably contains a plurality of holes. The number of holes in thespinneret and their arrangement is not critical, but it is desirable tomaximize the number of holes for economic reasons. The spinneret 4 cancontain as many as 100 or 1000, or more, and they may be arranged incircles, grids, or in any other desired arrangement. The spinneret 4 maybe constructed out of any materials that will not be severely degradedby the dope solution 2.

The spinning process of FIG. 1 employs “air-gap” spinning (alsosometimes known as “dry-jet” wet spinning) Dope solution 2 exits thespinneret 4 and enters a gap 8 (typically called an “air gap” althoughit need not contain air) between the spinneret 4 and a coagulation bath10 for a very short duration of time. The gap 8 may contain any fluidthat does not induce coagulation or react adversely with the dope, suchas air, nitrogen, argon, helium, or carbon dioxide. The dope filament 6proceeds across the air gap 8, and is immediately introduced into aliquid coagulation bath. Alternately, the fiber may be “wet-spun” (notshown). In wet spinning, the spinneret typically extrudes the fiberdirectly into the liquid of a coagulation bath and normally thespinneret is immersed or positioned beneath the surface of thecoagulation bath. Either spinning process may be used to provide fibersfor use in the processes of the invention. In some embodiments of thepresent invention, air-gap spinning is preferred.

The filament 6 is “coagulated” in the coagulation bath 10 containingwater or a mixture of water and sulfuric acid. If multiple filaments areextruded simultaneously, they may be combined into a multifilament yarnbefore, during or after the coagulation step. The term “coagulation” asused herein does not necessarily imply that the dope filament 6 is aflowing liquid and changes into a solid phase. The dope filament 6 canbe at a temperature low enough so that it is essentially non-flowingbefore entering the coagulation bath 10. However, the coagulation bath10 does ensure or complete the coagulation of the filament, i.e., theconversion of the polymer from a dope solution 2 to a substantiallysolid polymer filament 12. The amount of solvent, i.e., sulfuric acid,removed during the coagulation step will depend on the residence time ofthe filament 6 in the coagulation bath, the temperature of the bath 10,and the concentration of solvent therein. For example, using a 18 weightpercent copolymer/sulfuric acid solution at a temperature of about 23°C., a residence time of about one second will remove about 30 percent ofthe solvent present in the filament 6.

After the coagulation bath, the fiber may be contacted with one or morewashing baths or cabinets 14. Washes may be accomplished by immersingthe fiber into a bath or by spraying the fiber with the aqueoussolution. Washing cabinets typically comprise an enclosed cabinetcontaining one or more rolls which the yarn travels around a number oftimes, and across, prior to exiting the cabinet. As the yarn 12 travelsaround the roll, it is sprayed with a washing fluid. The washing fluidis continuously collected in the bottom of the cabinet and drainedtherefrom.

The temperature of the washing fluid(s) is preferably greater than 30°C. The washing fluid may also be applied in vapor form (steam), but ismore conveniently used in liquid form. Preferably, a number of washingbaths or cabinets are used. The residence time of the yarn 12 in any onewashing bath or cabinet 14 will depend on the desired concentration ofresidual sulfur in the yarn 12. In a continuous process, the duration ofthe entire washing process in the preferred multiple washing bath(s)and/or cabinet(s) is preferably no greater than about 10 minutes, morepreferably greater than about 5 seconds. In some embodiments theduration of the entire washing process is 20 seconds or more; in someembodiments the entire washing is accomplished in 400 seconds or less.In a batch process, the duration of the entire washing process can be onthe order of hours, as much as 12 to 24 hours or more.

Neutralization of the sulfuric acid in the yarn can occur in bath orcabinet 16. In some embodiments, the neutralization bath or cabinet mayfollow one or more washing baths or cabinets. Washes may be accomplishedby immersing the fiber into a bath or by spraying the fiber with theaqueous solution. Neutralization may occur in one bath or cabinet or inmultiple baths or cabinets. In some embodiments, preferred bases for theneutralization of sulfuric acid impurity include NaOH; KOH; Na₂CO₃;NaHCO₃; NH₄OH; Ca(OH)₂; K₂CO₃; KHCO₃; or trialkylamines, preferablytributylamine; other amines; or mixtures thereof. In one embodiment, thebase is water soluble. In some preferred examples the neutralizationsolution is an aqueous solution containing 0.01 to 1.25 mols of base perliter, preferably 0.01 to 0.5 mols of base per liter. The amount ofcation is also dependent on the time and temperature of exposure to thebase and the washing method. In some preferred embodiments, the base isNaOH or Ca(OH)₂. After treating the fiber with base, the processoptionally may include the step of contacting the yarn with a washingsolution containing water or an acid to remove all or substantially allexcess base. This washing solution can be applied in one or more washingbaths or cabinets 18.

After washing and neutralization, the fiber or yarn 12 may be dried in adryer 20 to remove water and other liquids. One or more dryers may beused. In certain embodiments, the dryer may be an oven which uses heatedair to dry the fibers. In other embodiments, heated rolls may be used toheat the fibers. The fiber is heated in the dryer to a temperature of atleast about 20° C. but less than about 100° C. until the moisturecontent of the fiber is 20 weight percent of the fiber or less. In someembodiments the fiber is heated to 85° C. or less. In some embodimentsthe fiber is heated under those conditions until the moisture content ofthe fiber is 14 weight percent of the fiber or less. The inventors havediscovered that low temperature drying is a preferred route to improvedfiber strength. Specifically, the inventors have found that the bestfiber strength properties are achieved when the first drying step (i.e.heated roll, heated atmosphere as in an oven, etc.) experienced by thenever-dried yarn is conducted at gentle temperatures not normally usedin continuous processes used to dry high strength fibers on commercialscale. It is believed that the copolymer fiber has more affinity towater than PPD-T homopolymer; this affinity slows the diffusion rate ofwater out of the polymer during drying and consequently if thenever-dried yarn is directly exposed to typical high dryingtemperatures, generally used to created a large thermal driving forceand reduce drying time, irreparable damage to the fiber occurs resultingin lower fiber strength. In some embodiments, the fiber is heated atleast to about 30° C.; in some embodiments the fiber is heated at leastto about 40° C.

The dryer residence time is less than ten minutes and is preferably lessthan 180 seconds. The dryer can be provided with a nitrogen or othernon-reactive atmosphere. The drying step typically is performed atatmospheric pressure. If desired, however, the step may be performedunder reduced pressure. In one embodiment, the filaments are dried undera tension of at least 0.1 gpd, preferably a tension of 2 gpd or greater.

Following the drying step, the fiber is preferably further heated to atemperature of at least 350° C. in, for instance, a heat setting device22. One or more devices may be utilized. For example, such processingmay be done in a nitrogen purged tube furnace 22 for increasing tenacityand/or relieving the mechanical strain of the molecules in thefilaments. In some embodiments, the fiber or yarn is heated to atemperature of at least 400° C. In one embodiment, the filaments arefurther under a tension of 1 gpd or less, using only enough tension toadvance the yarn through the heating device.

In some embodiments, the heating is a multistep process. For example, ina first step the fiber or yarn may heated at a temperature of 200 to360° C. at a tension of at least 0.2 cN/dtex, followed by a secondheating step where the fiber or yarn is heated at a temperature of 370to 500° C. at a tension of less than 1 cN/dtex.

Finally, the yarn 12 is wound up into a package on a windup device 24.Rolls, pins, guides, and/or motorized devices 26 are suitably positionedto transport the filament or yarn through the process. Such devices arewell known in the art and any suitable device may be utilized.

Molecular weights of polymers are typically monitored by, and correlatedto, one or more dilute solution viscosity measurements. Accordingly,dilute solution measurements of the relative viscosity (“V_(rel)” or“η_(rel)” or “n_(rel)”) and inherent viscosity (“V_(inh),” or “η_(inh)”or “n_(inh)”) are typically used for monitoring polymer molecularweight. The relative and inherent viscosities of dilute polymersolutions are related according to the expressionV _(inh)=ln(V _(rel))/C,where ln is the natural logarithm function and C is the concentration ofthe polymer solution. V_(rel) is a unitless ratio, thus V_(inh), isexpressed in units of inverse concentration, typically as deciliters pergram (“dl/g”).

The invention is further directed, in part, to fabrics that includefilaments or yarns of the present invention, and articles that includefabrics of the present invention. For purposes herein, “fabric” meansany woven, knitted, or non-woven structure. By “woven” is meant anyfabric weave, such as, plain weave, crowfoot weave, basket weave, satinweave, twill weave, and the like. By “knitted” is meant a structureproduced by interlooping or intermeshing one or more ends, fibers ormultifilament yarns. By “non-woven” is meant a network of fibers,including unidirectional fibers (if contained within a matrix resin),felt, and the like.

“Fiber” means a relatively flexible, unit of matter having a high ratioof length to width across its cross-sectional area perpendicular to itslength. Herein, the term “fiber” is used interchangeably with the term“filament”. The cross section of the filaments described herein can beany shape, but are typically circular or bean shaped. Fiber spun onto abobbin in a package is referred to as continuous fiber. Fiber can be cutinto short lengths called staple fiber. Fiber can be cut into evensmaller lengths called floc. The term “yarn” as used herein includesbundles of filaments, also known as multifilament yarns; or towscomprising a plurality of fibers; or spun staple yarns. Yarn can beintertwined and/or twisted.

Test Methods

Yarn tenacity is determined according to ASTM D 885 and is the maximumor breaking stress of a fiber as expressed as either force per unitcross-sectional area, as in giga-Pascals (GPa), or in force per unitmass per length, as in grams per denier or grams per dtex.

Inherent viscosity is determined using a solution in which a polymer isdissolved in a concentrated sulfuric acid with a concentration of 96 wt% at a polymer concentration (C) of 0.5 g/dl and at a temperature of 25°C. Inherent viscosity is then calculated as In (t_(poly)/t_(solv))/Cwhere t_(poly) is the drop time for the polymer solution and t_(solv) isthe drop time of the pure solvent.

Percent sulfur is determined according to ASTM D4239 Method B.

Moisture content of the fiber was obtained by first weighing the fibersample, placing the sample in an oven at 300° C. for 20 minutes, thenimmediately re-weighing the sample. Moisture content is then calculatedby substracting the dried sample weight from the initial sample weightand dividing by the dried sample weight times 100.

Many of the following examples are given to illustrate variousembodiments of the invention and should not be interpreted as limitingit in any way. All parts and percentages are by weight unless otherwiseindicated.

EXAMPLES General

A copolymer was made by coplomerizing the monomerspara-phenylenediamine, 5(6)-amino-2-(p-aminophenyl)benzimidazole; andterephthaloyl dichloride. The molar ratio of5(6)-amino-2-(p-aminophenyl)benzimidazole to para-phenylenediamine was70:30 and the molar ratio of para-phenylenediamine and5(6)-amino-2-(p-aminophenyl)benzimidazole to terephthaloyl dichloridewas 1:1. A spin solution of the copolymer in sulfuric acid was then madeand filaments were air gap spun from a spinneret into a coagulation bathto form a copolymer yarn. The yarn was comprised of 270 filaments havinga linear density of 3 denier per filament. The yarn was then washed withwater and wound onto bobbins. The inherent viscosity and the percentsulfur was measured on a sample of this yarn. The resulting yarn had asulfur content of 3.08 weight percent and an inherent viscosity of 3.54dl/g

The yarn was then fed from the bobbin to a series of 10 sequential washcabinet modules, each having a pair of washing rolls. The yarn waswashed through all 10 sequential modules using 20 spiral wraps aroundthe pair of rolls in each module. The wash liquid in the sixth andeighth modules was a 2% by weight aqueous sodium hydroxide. The otherwashes were with plain water. The wet yarn was then dried as shown inthe following examples.

Comparative Example A

A sample of the wet yarn was run through a high temperature oven havingrolls. The first heated roll the wet yarn contacted had a surfacetemperature of 180° C. The yarn was dried at that temperature.

Example 1

Several samples of the wet yarn were first run across the lowtemperature dryer rolls operating at a constant surface temperature andthen run through the high temperature oven having rolls mentioned in theComparative Example. Individual separate runs were made at differentdryer roll temperatures followed by high temperature drying at 180° C.in the roll oven. Specifically, separate samples of the wet yarn wererun through the dryer rolls operating at 25° C., 60° C., 70° C., 80° C.,90° C., 100° C., 110° C., and 120° C. In other words, the first heatedroll the wet yarn contacted was 25° C., 60° C., 70° C., 80° C., 90° C.,100° C., 110° C., and 120° C. The total residence time on the dryerrolls was 4.5 minutes and then passed through the coupled roll oven tocomplete drying.

Example 2

The set of yarns from Example 1 and the yarn from Comparative Example Awere then each individually and identically heat treated in a refractorystyle tube oven operating at a maximum temperature of 400 C. Each yarnwas then tested for tenacity and then plotted versus the first rolltemperature experienced by the yarn as shown in Example 1. The relativetenacity of these yarns was then calculated using the followingequation; for convenience the highest measured tenacity was chosen asthe Reference Tenacity:Relative Tenacity=Actual Tenacity/Reference Tenacity

FIG. 2 is a graph of first roll temperature versus relative tenacity andillustrates that higher yarn tenacities result from controlling theinitial drying temperature experienced by the yarn.

Example 3

Example 1 and Example 2 can be repeated by drying the yarns using atension of at least 0.1 gpd, followed by heat treating the same yarnsusing a tension of less than 1 gpd with similar result.

What is claimed:
 1. A process for reducing water in never-dried fibercomprising copolymer derived from the copolymerization ofpara-phenylenediamine, 5(6)-amino-2-(p-aminophenyl)benzimidazole, andterephthaloyl dichloride, the process having the following steps in acontinuous process: (a) a step of drying a never-dried fiber having atleast 0.1 wt % sulfur at 150° C. or less until the moisture content ofthe fiber is less than 60 weight percent; and (b) a step of furtherdrying the fiber above 150° C. while the moisture content of the fiberis less than 60 weight percent; the fiber being further heated to atleast 350° C. in either an additional continuous or separate step. 2.The process of claim 1 where in step (a) the fiber is dried at 100° C.or less.
 3. The process of claim 2 where in step (a) the fiber is driedat 50° C. or less.
 4. The process of claim 1 where in step (a) the fiberis dried until the moisture content is less than 50%.
 5. The process ofclaim 4 where in step (a) the fiber is dried until the moisture contentis less than 40%.
 6. The process of claim 2 wherein after step (a), thefiber is further dried at an additional step at less than 150° C. untilmoisture content is less than 50%, prior to step (b).
 7. The process ofclaim 6 wherein after step (a) the fiber is further dried at anadditional step at less than 150° C. until moisture content is less than40%, prior to step (b).
 8. The process of claim 1, wherein the fiber isheated above 400° C. in the last step.
 9. The process of claim 1,wherein the fiber is heated in step (a) under a tension of at least 0.1gpd.
 10. The process of claim 1, wherein the fiber is heated in the laststep under a tension of less than 1 gpd.
 11. The process of claim 1,wherein the ratio of moles of 5(6)-amino-2-(p-aminophenyl)benzimidazoleto the moles of para-phenylenediamine is 30/70 to 85/15.
 12. The processof claim 11 wherein the ratio is 45/55 to 85/15.
 13. The process ofclaim 1, wherein the fiber is heated in an oven in step (a).
 14. Theprocess of claim 1, wherein said fiber is heated by contacting saidfilaments with a hot surface.
 15. A process for producing filamentscomprising a copolymer derived from the copolymerization ofpara-phenylenediamine, 5(6)-amino-2-(p-aminophenyl)benzimidazole, andterephthaloyl dichloride, including the following steps in a continuousprocess: (a) a step of spinning filaments into a coagulation bath from asulfuric acid solution of the copolymer; (b) a step of contacting thefilaments with one or more of (i) wash and (ii) neutralization fluid;(c) a step of drying the filaments having at least 0.1 wt % sulfur at150° C. or less until the moisture content of the filaments is less than60 weight percent; (d) an optional step of further drying the filamentsat a temperature higher than step (c); (e) a step of further drying thefilaments above 150° C. while the moisture content of the fiber is lessthan 60 weight percent; the filaments being further heated to at least350° C. in either an additional continuous or separate step.
 16. Theprocess of claim 15 wherein the filaments are heated above 400° C. inthe last step.
 17. The process of claim 15 wherein the filaments areheated in step (c) under a tension of at least 0.1 gpd.
 18. The processof claim 15 wherein the filaments are heated in the last step under atension of less than 1 gpd.
 19. The process of claim 15 wherein saidfilaments are heated by contacting said filaments with a hot surface.